WO2015029415A1 - 光発電デバイスおよびその製造方法 - Google Patents

光発電デバイスおよびその製造方法 Download PDF

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Publication number
WO2015029415A1
WO2015029415A1 PCT/JP2014/004360 JP2014004360W WO2015029415A1 WO 2015029415 A1 WO2015029415 A1 WO 2015029415A1 JP 2014004360 W JP2014004360 W JP 2014004360W WO 2015029415 A1 WO2015029415 A1 WO 2015029415A1
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photoelectric conversion
conversion module
module substrate
organic photoelectric
layer
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PCT/JP2014/004360
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English (en)
French (fr)
Japanese (ja)
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清茂 児島
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日本ゼオン株式会社
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Priority to JP2015533988A priority Critical patent/JPWO2015029415A1/ja
Priority to CN201480045283.XA priority patent/CN105474338A/zh
Priority to KR1020167003569A priority patent/KR20160048069A/ko
Priority to US14/911,511 priority patent/US20160196928A1/en
Priority to EP14840729.9A priority patent/EP3041009A4/en
Publication of WO2015029415A1 publication Critical patent/WO2015029415A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2068—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/0029—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
    • H01L31/046—PV modules composed of a plurality of thin film solar cells deposited on the same substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a photovoltaic device formed by laminating and connecting two or more organic photoelectric conversion module substrates, and a method for manufacturing the photovoltaic device.
  • a photoelectric conversion module that converts light energy such as solar energy into electric energy
  • a photoelectric conversion module using a solar cell (cell) as a photoelectric conversion element is known.
  • the solar cell a silicon (Si) solar cell or the like is used.
  • organic solar cells such as dye-sensitized solar cells and organic thin-film solar cells have attracted attention as solar cells that replace Si-based solar cells and the like.
  • dye-sensitized solar cells can be expected to be lighter than Si-based solar cells, etc., can be stably generated in a wide illuminance range, and are relatively inexpensive without requiring large-scale equipment. It has attracted particular attention because it can be manufactured using materials.
  • This dye-sensitized solar cell usually has a structure in which a photoelectrode 10, an electrolyte layer 20, and a counter electrode 30 are arranged in this order as shown in FIG.
  • the sensitizing dye in the photoelectrode 10 when excited by receiving light, the electrons of the sensitizing dye are taken out, and the taken-out electrons exit from the photoelectrode 10 and are externally supplied. It moves to the counter electrode 30 through the circuit 40 and further moves to the electrolyte layer 20.
  • reference numeral 10a is a photoelectrode substrate
  • 10b is a porous semiconductor fine particle layer
  • 10c is a sensitizing dye layer
  • 10d and 30a are supports
  • 10e and 30c are conductive films
  • 30b is a catalyst layer.
  • dye-sensitized solar cells have lower photoelectric conversion efficiency and inferior power generation efficiency than Si-based solar cells and the like. Therefore, a plurality of dye-sensitized solar cells are connected to each other to improve power generation.
  • Patent Documents 1 and 2 a plurality of dye-sensitized solar cells are stacked, and dye-sensitized solar cells adjacent in the stacking direction are electrically connected to each other.
  • a solar cell module is disclosed.
  • the present invention has been developed to solve the above-described problems, and an object thereof is to provide a photovoltaic device having a high power generation amount. Another object of the present invention is to provide an efficient method for manufacturing such a photovoltaic device.
  • the inventors have intensively studied to develop a photovoltaic device having a high power generation amount.
  • 20 to 80% of the area of each organic photoelectric conversion module substrate is used as the photoelectric conversion element portion, and has passed through the upper module substrate. It was found that the amount of power generation is increased by connecting light so that it can be captured and photoelectrically converted by the lower module substrate.
  • the gist configuration of the present invention is as follows. 1. Two or more organic photoelectric conversion module substrates having at least one photoelectric conversion element are stacked and connected, A photovoltaic device characterized in that 20 to 80% of the area of the organic photoelectric conversion module substrate is the photoelectric conversion element portion.
  • the organic photoelectric conversion module substrate further comprises an opening, Between the organic photoelectric conversion module substrates adjacent to each other in the stacking direction, at least a part of the opening of the organic photoelectric conversion module substrate positioned on one side of the stacking direction and the organic photoelectric conversion module substrate positioned on the other side of the stacking direction 2.
  • the photovoltaic device according to 1 above wherein at least a part of the photoelectric conversion element section of the first and second photoelectric conversion element sections overlaps in the stacking direction.
  • the unit further includes an opening, and when the two units are overlapped by folding between adjacent units, at least a part of the opening of the unit located on one side in the stacking direction between the units adjacent to each other in the stacking direction;
  • a photovoltaic device having a high power generation amount can be obtained.
  • the photovoltaic device of the present invention is formed by stacking and electrically connecting two or more organic photoelectric conversion module substrates each having at least one photoelectric conversion element.
  • a sectional view showing an example of the photovoltaic device of the present invention is shown in FIG.
  • FIG. 2 in the photovoltaic device of the present invention, there are usually three modes as the stacked form of the organic photoelectric conversion module substrate depending on the position of the current collecting wiring. As shown in FIG.
  • the current collecting wiring usually exists in a state where it is in contact with only one of the upper and lower base materials of the organic photoelectric conversion module substrate, but may be in contact with both base materials. There is no difference depending on the position of the electric wiring, and the stacked form of the organic photoelectric conversion module substrate is one mode.
  • reference numeral 50 denotes a photovoltaic device
  • 50a denotes a side wall
  • 60 denotes an organic photoelectric conversion module substrate
  • 60a denotes a base material
  • 60b denotes a photoelectric conversion element
  • 60c denotes a current collector wiring
  • 60d denotes an opening. .
  • the substrate region where the photoelectric conversion element is not arranged is usually an opening (including a current collecting wiring portion).
  • the opening may be a cavity, but is usually preferably sealed with a transparent resin as described later.
  • the organic photoelectric photoelectric layer positioned on one side in the stacking direction between the organic photoelectric conversion module substrates adjacent to each other in the stacking direction. It is preferable that at least a part of the opening of the conversion module substrate and at least a part of the photoelectric conversion element of the organic photoelectric conversion module substrate located on the other side in the stacking direction are stacked so as to overlap in the stacking direction. Thereby, the irradiated light can efficiently reach the lower module substrate, and the effective area of the photoelectric conversion element contributing to the photoelectric conversion can be increased to improve the power generation amount.
  • the organic photoelectric conversion module substrates adjacent to each other in the stacking direction at least a part of the opening of the organic photoelectric conversion module substrate positioned on one side of the stacking direction and the organic photoelectric conversion positioned on the other side of the stacking direction At least part of the photoelectric conversion elements on the module substrate overlap in the stacking direction so that the overlapping area between the photoelectric conversion elements on the upper module substrate and the module substrate below the upper module substrate.
  • the area is preferably 0 to 50%, more preferably 0 to 30%, the effective area of the photoelectric conversion element contributing to photoelectric conversion can be sufficiently increased, and a high power generation amount can be obtained.
  • the photoelectric conversion elements on the upper module board and the module board below it partially overlap, the light incident obliquely from the opening of the upper module board is captured by the photoelectric conversion elements on the lower module board This is preferable.
  • substrate in the relationship between a 1st layer and a 2nd layer, The first layer is the upper module substrate, the second layer is the lower module substrate, and in the relationship between the second layer and the third layer, the second layer is the upper module substrate and the third layer is the lower module substrate.
  • the organic photoelectric conversion module substrate has four or more layers.
  • the number of stacked organic photoelectric conversion module substrates is preferably about 2 to 5 layers from the viewpoint of optimizing the power generation amount and the manufacturing cost.
  • the distance a between the organic photoelectric conversion module substrates is preferably 10 nm to from the viewpoint of efficiently capturing the incident light with the lower module substrate. A range of 5 mm is preferable, and a range of 100 nm to 3 mm is more preferable.
  • the organic photoelectric conversion module substrate constituting the photovoltaic device of the present invention includes at least one photoelectric conversion element.
  • an organic photoelectric conversion module substrate includes a plurality of photoelectric conversion elements arranged in parallel on a base material as a support, and the photoelectric conversion elements are connected in series or in parallel by current collecting wiring. Are electrically connected to each other (part of the wiring is not shown).
  • region in which the photoelectric conversion element is not normally installed becomes an opening part (a current collection wiring part is included).
  • a transparent base material As said base material, it is preferable to use a transparent base material from a viewpoint of improving the light transmittance of the photoelectric conversion element and opening part of an organic type photoelectric conversion module board
  • a transparent substrate include a transparent resin substrate made of a transparent resin described later, a glass substrate, and the like.
  • transparent as used in the present invention means light transmittance: 70% or more (preferably 80% or more).
  • the light transmittance is the total light transmittance measured according to JIS K7361-1.
  • the thickness of the transparent substrate is preferably in the range of 0.01 to 10 mm from the viewpoint of the balance between light transmittance and strength.
  • the organic photoelectric conversion module substrate used in the present invention secures a power generation amount per one layer of the module substrate and transmits light from the upper module substrate. From the viewpoint of increasing the effective area of the photoelectric conversion element that contributes to photoelectric conversion by securing a sufficient amount of light incident on the lower module substrate, thereby improving the power generation amount of the device, the organic photoelectric conversion module substrate It is necessary to make 20 to 80% of the area a photoelectric conversion element portion. From the viewpoint of securing device performance and facilitating the formation of photoelectric conversion elements and current collector wiring to reduce the manufacturing cost, it is preferably 35 to 65%, more preferably 40 to 60%.
  • the ratio of the photoelectric conversion element portion to the area of the organic photoelectric conversion module substrate is not necessarily the same between the upper module substrate and the lower module substrate.
  • the dye-sensitized solar cell usually has a structure in which a photoelectrode (transparent electrode) 10, an electrolyte layer 20, and a counter electrode 30 are arranged in this order.
  • the photoelectrode 10 was formed by adsorbing a sensitizing dye on the surface of the photoelectrode substrate 10a, the porous semiconductor fine particle layer 10b formed thereon, and the porous semiconductor fine particle layer. And a sensitizing dye layer 10c.
  • the photoelectrode substrate 10a plays a role of supporting the porous semiconductor fine particle layer 10b and the like and a role of a current collector.
  • the photoelectrode substrate 10a is made of, for example, a composite resin oxide such as indium-tin oxide (ITO) or indium-zinc oxide (IZO) on a transparent resin base material or glass base material to be the support 10d.
  • ITO indium-tin oxide
  • IZO indium-zinc oxide
  • the base material of the organic photoelectric conversion module substrate constituting the photovoltaic device of the present invention normally functions as the support 10d.
  • cycloolefin polymer COP
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • SPS syndiotactic polystyrene
  • PPS polyphenylene sulfide
  • PC polycarbonate
  • synthetic resins such as polyarylate (PAr), polysulfone (PSF), polyester sulfone (PES), polyetherimide (PEI), and transparent polyimide (PI).
  • the porous semiconductor fine particle layer 10b is a porous layer containing semiconductor fine particles.
  • the semiconductor fine particles include metal oxide particles such as titanium oxide, zinc oxide, and tin oxide.
  • the porous semiconductor fine particle layer can be formed by a known method such as a press method, a hydrothermal decomposition method, an electrophoretic electrodeposition method, or a binder-free coating method.
  • the sensitizing dye layer 10c is a layer in which a compound (sensitizing dye) that can be excited by light and pass electrons to the porous semiconductor fine particle layer 10b is adsorbed on the surface of the porous semiconductor fine particle layer 10b.
  • the sensitizing dye used may be the same or different between the dye-sensitized solar cells forming the photoelectric conversion element of the present invention.
  • Sensitizing dyes include organic dyes such as cyanine dyes, merocyanine dyes, oxonol dyes, xanthene dyes, squarylium dyes, polymethine dyes, coumarin dyes, riboflavin dyes, perylene dyes; phthalocyanine complexes of metals such as iron, copper, ruthenium, and porphyrins. Metal complex dyes such as complexes; and the like.
  • the sensitizing dye layer 10c is a known method such as a method of immersing the porous semiconductor fine particle layer 10b in a sensitizing dye solution or a method of applying a sensitizing dye solution onto the porous semiconductor fine particle layer 10b. Can be formed.
  • the photoelectrode is not limited to the one shown in FIG. 1, and may be any electrode that can emit light to the external circuit 40 by receiving light.
  • Electrolyte layer The electrolyte layer 20 is a layer for separating the photoelectrode 10 and the counter electrode 30 and efficiently performing charge transfer.
  • the electrolyte layer 20 usually contains a supporting electrolyte, a redox pair (a pair of chemical species that can be reversibly converted into an oxidized form and a reduced form in a redox reaction), a solvent, and the like.
  • Examples of the supporting electrolyte include salts containing cations such as lithium ions, imidazolium ions, and quaternary ammonium ions.
  • the oxidation-reduction pair is not particularly limited as long as it can reduce the oxidized sensitizing dye. Chlorine compound-chlorine, iodine compound-iodine, bromine compound-bromine, thallium ion (III) -thallium ion (I ), Ruthenium ion (III) -ruthenium ion (II), copper ion (II) -copper ion (I), iron ion (III) -iron ion (II), cobalt ion (III) -cobalt ion (II), Examples thereof include vanadium ion (III) -vanadium ion (II), manganate ion-permanganate ion, ferricyanide-ferrocyanide, quinone-hydroquinone, fumaric acid-succinic acid, and the like.
  • the solvent examples include acetonitrile, methoxyacetonitrile, methoxypropionitrile, N, N-dimethylformamide, ethylmethylimidazolium bistrifluoromethylsulfonylimide, propylene carbonate, and the like, which are solvents for forming an electrolyte layer of a solar cell.
  • the electrolyte layer 20 is obtained by applying a solution (electrolyte) containing the constituent components onto the photoelectrode 10, producing a cell having the photoelectrode 10 and the counter electrode 30, and injecting the electrolyte into the gap. Can be formed.
  • the counter electrode 30 is formed, for example, by forming a conductive film 30c on a support 30a and forming a catalyst layer 30b on the conductive film 30c.
  • the support 30a and the conductive film 30c include those similar to the above-described photoelectrode substrate 10a.
  • the catalyst layer 30b is provided arbitrarily and functions as a catalyst when electrons are transferred from the counter electrode to the electrolyte layer, and is usually formed of a platinum thin film.
  • the base material of the organic type photoelectric conversion module substrate which comprises the photovoltaic device of this invention may function as this support body 30a.
  • the catalyst layer 30b has electroconductivity, although the electrically conductive film 30c is not necessarily required, it is preferable to provide the electrically conductive film 30c from a viewpoint of ensuring more favorable electricity supply.
  • the above-described catalyst layer of the counter electrode includes carbon nanotubes or metal nanoparticle-supported carbon nanotubes, and the photoelectrode and the counter electrode. It is extremely advantageous to apply a carbon nanotube or a conductor containing a carbon nanotube and a metal nanostructure to the conductive film. This is because the catalytic activity and conductivity can be improved compared to the case of using a composite metal oxide such as a conventional platinum thin film or indium-tin oxide (ITO), and the power generation efficiency as a battery is also improved.
  • a composite metal oxide such as a conventional platinum thin film or indium-tin oxide (ITO)
  • the organic photoelectric conversion module substrate can be provided with a large opening, and the battery can be manufactured by a roll-to-roll method, which can greatly improve the productivity and increase the power generation amount of the device. This is because the ease of manufacturing can be improved and the manufacturing cost can be reduced.
  • the carbon nanotube and the metal nanoparticle-supporting carbon nanotube, and the conductor containing the carbon nanotube or the carbon nanotube and the metal nanostructure will be described.
  • Carbon nanotubes and metal nanoparticle-supported carbon nanotubes A platinum thin film is usually used for the catalyst layer of the counter electrode, but carbon nanotubes, particularly average diameter (Av) and diameter standard, are used as alternative materials.
  • a carbon nanotube satisfying a deviation ( ⁇ ) of 0.60> 3 ⁇ / Av> 0.20 (preferably 0.60> 3 ⁇ / Av> 0.50) (hereinafter also referred to as carbon nanotube (A)), and this carbon
  • the accuracy of workability is greatly improved and the production of a high-speed coating / processed film by roll-to-roll becomes easy, which is extremely advantageous for mass production.
  • the catalytic activity can be increased, and as a result, the power generation efficiency as a battery can be increased. This is because the light transmittance of the module substrate can be enhanced.
  • the “carbon nanotube (A)” here is a general term for a set of predetermined carbon nanotubes constituting the carbon nanotube, and the “diameter” means an outer diameter of the predetermined carbon nanotube.
  • the average diameter (Av) and the standard deviation of diameter ( ⁇ ) are the average value and standard deviation when measuring the diameter of 100 randomly selected carbon nanotubes under observation with a transmission electron microscope. (The average length described later is also obtained as an average value by measuring the length in the same manner.)
  • the carbon nanotube (A) usually has a normal distribution when plotted with the diameter measured as described above on the horizontal axis and the frequency on the vertical axis and approximated by Gaussian. used.
  • the average diameter (Av) of the carbon nanotube (A) is preferably 0.5 nm or more and 15 nm or less, and more preferably 1 nm or more and 10 nm or less from the viewpoint of obtaining excellent catalytic activity.
  • the average length of the carbon nanotube (A) is preferably 0.1 ⁇ m to 1 cm, more preferably 0.1 ⁇ m to 1 mm.
  • the specific surface area of the carbon nanotube (A) is preferably 100 to 2500 m 2 / g, more preferably 400 to 1600 m 2 / g.
  • the specific surface area of the carbon nanotube (A) can be obtained by a nitrogen gas adsorption method.
  • the carbon nanotubes constituting the carbon nanotube (A) may be single-walled or multi-walled, but from the viewpoint of improving the activity of the catalyst layer, those of single-layer to five-layer are preferable. A single layer is more preferable.
  • the carbon nanotube constituting the carbon nanotube (A) may have a functional group such as a carboxyl group introduced on the surface.
  • the functional group can be introduced by a known oxidation treatment method using hydrogen peroxide, nitric acid or the like.
  • the carbon nanotube which comprises a carbon nanotube (A) has a some micropore.
  • the carbon nanotube preferably has micropores having a pore diameter smaller than 2 nm, and the abundance thereof is a micropore volume determined by the following method, and is preferably 0.4 mL / g or more, more preferably 0.8. It is 43 mL / g or more, More preferably, it is 0.45 mL / g or more, and as an upper limit, it is about 0.65 mL / g normally. It is preferable that the carbon nanotube has the above micropores from the viewpoint of improving the catalytic activity.
  • micropore volume can be adjusted, for example, by appropriately changing the carbon nanotube preparation method and preparation conditions.
  • Vp is a nitrogen adsorption / desorption isotherm at a liquid nitrogen temperature (77 K) of the carbon nanotube
  • P is the measurement pressure at the time of adsorption equilibrium
  • P0 is the saturated vapor pressure of liquid nitrogen at the time of measurement
  • M is the molecular weight of adsorbate (nitrogen) 28.010
  • ⁇ is the adsorbate (nitrogen).
  • the micropore volume can be easily determined using, for example, “BELSORP (registered trademark) -mini” (manufactured by Nippon Bell Co., Ltd.).
  • the carbon nanotube (A) having the above characteristics is, for example, a substrate (hereinafter referred to as “CNT production”) having a carbon nanotube production catalyst layer (hereinafter, also referred to as “CNT production catalyst layer”) on the surface.
  • CNT production catalyst layer a carbon nanotube production catalyst layer
  • CVD chemical vapor deposition
  • a small amount of oxidizing agent is added to the system.
  • formation of the catalyst layer on the surface of the substrate is performed by a wet process.
  • the carbon nanotube obtained by this super-growth method is hereinafter referred to as SGCN. May be referred to.).
  • metal nanoparticles may be supported on the carbon nanotube (A), and in that case, an improvement in catalytic effect is expected.
  • Examples of the metal nanoparticles include nanoparticles of metals in Groups 6 to 14 of the periodic table.
  • the metals of Groups 6 to 14 of the periodic table include Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Ag, Cd, Sn, Sb, W, Re, Ir , Pt, Au, Pb and the like.
  • Fe, Co, Ni, Ag, W, Ru, Pt, Au, and Pd are preferable because a highly versatile oxidation-reduction catalyst can be obtained.
  • the said metal can be used individually by 1 type or in combination of 2 or more types.
  • the average particle diameter of the metal nanoparticles is preferably 0.5 to 15 nm, and the standard deviation of the particle diameter is preferably 1.5 nm or less.
  • the amount of metal nanoparticles supported is not particularly limited, it is preferably 1 part by mass or more per 100 parts by mass of the carbon nanotube (A). More excellent catalytic activity can be obtained when the supported amount of metal nanoparticles is 1 part by mass or more. Although it is considered that the greater the amount of supported metal nanoparticles, the higher the catalytic activity.
  • the upper limit of the supported amount of metal nanoparticles is carbon nanotubes (A ) Usually, it is preferable to be 30,000 parts by mass or less per 100 parts by mass.
  • the method for supporting the metal nanoparticles on the carbon nanotube is not particularly limited.
  • a known method for generating metal nanoparticles by reducing the metal precursor in the presence of the carbon nanotube (A) is used.
  • Metal nanoparticles can be supported on carbon nanotubes.
  • a dispersion containing water, carbon nanotubes (A), and a dispersant is prepared, and after adding a metal precursor, the solvent is distilled off, and the metal precursor is further heated under a hydrogen stream.
  • a dispersion containing carbon nanotubes (A) is prepared, this dispersion is applied onto a support, and the resulting coating film is dried. Good.
  • Solvents used for preparing the dispersion include water; alcohols such as methyl alcohol, ethyl alcohol and propyl alcohol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran, dioxane and diglyme; N, N-dimethylformamide; And amides such as N, N-dimethylacetamide, N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone; sulfur-containing solvents such as dimethyl sulfoxide and sulfolane; These solvents can be used alone or in combination of two or more.
  • the dispersion may further contain a binder, a conductive aid, a dispersant, a surfactant, and the like. These may be appropriately known ones.
  • the dispersion can be obtained, for example, by mixing the carbon nanotubes (A) and, if necessary, other components in a solvent to disperse the carbon nanotubes.
  • a method using a nanomizer, an optimizer, an ultrasonic disperser, a ball mill, a sand grinder, a dyno mill, a spike mill, a DCP mill, a basket mill, a paint conditioner, a high-speed stirring device, or the like may be used. .
  • dipping method roll coating method, gravure coating method, knife coating method, air knife coating method, roll knife coating method, die coating method, screen printing method, spray coating method, gravure method
  • An offset method or the like may be employed.
  • a hot air drying method, a hot roll drying method, an infrared irradiation method, or the like may be employed for drying the coating film.
  • the drying temperature is not particularly limited, but is usually room temperature to 200 ° C.
  • the drying time is not particularly limited, but is usually 0.1 to 150 minutes.
  • the content of the carbon nanotube (A) in the dispersion is not particularly limited, but is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass in the entire dispersion.
  • Conductor containing carbon nanotube or carbon nanotube and metal nanostructure As a conductive film for the photoelectrode and the counter electrode, a composite metal such as indium-tin oxide (ITO), indium-zinc oxide (IZO), etc. An oxide or the like is generally used.
  • a conductor containing the above-described carbon nanotube (A) or carbon nanotube (A) and a metal nanostructure (hereinafter referred to as a conductor layer) It is preferable to adopt (also referred to as (I)). This is because such a conductive film can be formed by applying and drying a dispersion of carbon nanotubes or a dispersion of carbon nanotubes and metal nanostructures.
  • the metal nanostructure described above is a microstructure made of a metal or a metal compound, and is used here as a conductor.
  • the metal or metal compound constituting the metal nanostructure is not particularly limited as long as it has conductivity.
  • metals such as copper, silver, platinum, and gold; metal oxides such as indium oxide, zinc oxide, and tin oxide; aluminum zinc oxide (AZO), indium tin oxide (ITO), and indium zinc oxide (IZO) And the like, and the like.
  • silver or platinum is preferable because excellent conductivity and transparency can be easily obtained.
  • examples of the metal nanostructure include metal nanoparticles, metal nanowires, metal nanorods, and metal nanosheets.
  • metal nanoparticles are particulate structures having an average particle size on the nanometer scale.
  • the average particle diameter of metal nanoparticles (average particle diameter of primary particles) is not particularly limited, but is preferably 10 to 300 nm. When the average particle diameter is within the above range, a conductive film having excellent conductivity and transparency can be easily obtained.
  • the average particle diameter of the metal nanoparticles can be calculated by measuring the particle diameters of 100 randomly selected metal nanoparticles using a transmission electron microscope. In addition, the size of other metal nanostructures described below can be obtained by the same method.
  • metal nanoparticles can be prepared by mixing a polyol method for synthesizing metal nanoparticles by reducing an organic complex with a polyhydric alcohol, a reverse micelle solution containing a reducing agent, and a reverse micelle solution containing a metal salt. It can be obtained by using a known method such as a reverse micelle method for synthesizing particles.
  • the metal nanowire is a linear structure having an average diameter of nanometer scale and an aspect ratio (length / diameter) of 10 or more.
  • the average diameter of the metal nanowire is not particularly limited, but is preferably 10 to 300 nm.
  • the average length of the metal nanowire is not particularly limited, but is preferably 3 ⁇ m or more. When the average diameter and the average length are within the above ranges, a conductive film having excellent conductivity and transparency can be easily obtained.
  • the metal nanowire is, for example, a method in which an applied voltage or current is applied to the precursor surface from the tip of the probe, the metal nanowire is drawn out at the probe tip, and the metal nanowire is continuously formed (Japanese Patent Laid-Open No. 2004-223893) ) And a method of reducing nanofibers composed of metal complexed peptide lipids (Japanese Patent Laid-Open No. 2002-266007).
  • the metal nanorod is a cylindrical structure having an average diameter of nanometer scale and an aspect ratio (length / diameter) of 1 or more and less than 10.
  • the average diameter of the nanorods is not particularly limited, but is preferably 10 to 300 nm.
  • the average length of the nanorods is not particularly limited, but is preferably 10 to 3000 nm. When the average diameter and the average length are within the above ranges, a conductive film having excellent conductivity and transparency can be easily obtained.
  • the metal nanorod can be obtained by using a known method such as an electrolytic method, a chemical reduction method, or a photoreduction method.
  • the metal nanosheet is a sheet-like structure having a thickness on the nanometer scale.
  • the thickness of the metal nanosheet is not particularly limited, but is preferably 1 to 10 nm.
  • the size of the metal nanosheet is not particularly limited, but preferably the length of one side is 0.1 to 10 ⁇ m. When the thickness and the length of one side are within the above ranges, a conductive film having excellent conductivity and transparency can be easily obtained.
  • the metal nanosheet can be obtained by using a known method such as a method of peeling a layered compound, a chemical vapor deposition method, a hydrothermal method or the like.
  • metal nanowires because excellent conductivity and transparency are easily obtained.
  • a metal nanostructure can be used individually by 1 type or in combination of 2 or more types.
  • the content of the metal nanostructure in the conductor layer (I) is not particularly limited, but is preferably 0.0001 to 0.05 mg / cm 2 .
  • the content of the carbon nanotube (A) in the conductor layer (I) is preferably 1.0 ⁇ 10 ⁇ 6 to 30 mg / cm 2 .
  • the thickness of the conductor layer (I) is not particularly limited, but is usually 100 nm to 1 mm. If the thickness of the conductor layer is within the above range, good conductivity and transparency can be obtained.
  • the conductor layer (I) may contain other components such as a binder, a conductive auxiliary agent, a dispersant, and a surfactant as long as the conductivity and transparency are not affected.
  • the content of the metal nanostructure in the conductor layer (II) is not particularly limited, but is preferably 0.0001 to 0.2 mg / cm 2 . By setting the content of the metal nanostructure within the above range, conductivity and transparency are further improved.
  • the thickness of the conductor layer (II) is not particularly limited, but is usually 30 nm to 1 mm. By setting the thickness of the conductor layer (II) within the above range, good conductivity and transparency can be obtained.
  • the conductor layer (II) may contain other components in addition to the metal nanostructure as long as the conductivity and transparency are not affected. Examples of the other components include those shown as the other components in the conductor layer (I).
  • it may have other layers such as a hard coat layer, a gas barrier layer, and an adhesive layer as long as the conductivity and transparency are not affected.
  • These layers can be formed by a conventionally known method.
  • the above-described conductor layer (I) is obtained by, for example, preparing a dispersion containing the metal nanostructure and the carbon nanotube (A) and applying the dispersion onto a support that is a base material.
  • the obtained coating film is dried to form a conductor layer.
  • the dispersion may be adjusted in the same manner as in the formation of the catalyst layer.
  • Application and drying may be performed in the same manner as in the formation of the catalyst layer.
  • carbon nanotubes or metal nanoparticle-supporting carbon nanotubes are used as the catalyst layer of the counter electrode of the dye-sensitized solar cell, and carbon is used as the conductive film of the photo electrode and the counter electrode.
  • a conductor containing nanotubes or carbon nanotubes and metal nanostructures manufacturing costs can be significantly reduced, and for such catalyst layers and conductive films, a dispersion in which carbon nanotubes are dispersed can be applied. It can be formed by drying, its applicability is good, the accuracy of workability is greatly improved, and it is easy to manufacture high-speed coating and processed films by roll-to-roll, which is extremely advantageous for mass production. Become.
  • the catalytic activity and conductivity can be increased and the power generation efficiency of the battery can be increased as compared with the case where a conventional platinum thin film or indium-tin oxide (ITO) is used, so a large opening is provided. This is because the light transmittance of the module substrate can be enhanced while balancing the manufacturability.
  • ITO indium-tin oxide
  • the photovoltaic device of the present invention is not particularly limited, for example, the photoelectric conversion element as described above, so that the element occupies the area of the organic photoelectric conversion module substrate obtained in a predetermined ratio,
  • the organic photoelectric conversion module substrate is formed by arranging the photoelectric conversion elements in parallel on a transparent base material at regular intervals, and electrically connecting these photoelectric conversion elements by current collecting wiring. Two or more layers can be laminated and electrically connected.
  • what is necessary is just to follow a well-known method about formation of a photoelectric conversion element, patterning of current collection wiring, etc.
  • the yield is improved and, for example, if carbon nanotubes are used for the formation of the photoelectric conversion element, it is possible to manufacture in a roll-to-roll system, the manufacturing cost can be reduced, and the present invention can be stably and efficiently performed. Since two or more units of organic photoelectric conversion module substrates that are electrically connected to each other are formed on a transparent base material, the unit is folded between adjacent units. A method having a step of stacking and stacking two or more organic photoelectric conversion module substrates is particularly preferable.
  • FIG. 4 is a process diagram showing an example of the method of manufacturing the photovoltaic device of the present invention that is particularly preferable as described above.
  • the same organic photoelectric conversion module substrate as shown in FIG. 3 is used as one unit, and two units of the substrate are formed on the transparent base [(a)], and the two units are folded between adjacent units.
  • an organic photoelectric conversion module substrate located on one side in the stacking direction between the adjacent organic photoelectric conversion module substrates in the stacking direction By stacking two layers of organic photoelectric conversion module substrates [(b)], an organic photoelectric conversion module substrate located on one side in the stacking direction between the adjacent organic photoelectric conversion module substrates in the stacking direction
  • the photovoltaic device of the present invention is manufactured in which a part of the opening part of the organic photoelectric conversion module part of the organic photoelectric conversion module substrate located on the other side in the stacking direction overlaps in the stacking direction [( c)].
  • the units of the organic photoelectric conversion module substrate may be stacked in the opposite direction to that shown in FIG.
  • Example 1 After forming two organic photoelectric conversion module substrate units that are electrically connected to each other on a transparent substrate, the unit is folded between adjacent units, and both units are stacked, and two organic photoelectric conversion module substrates are stacked. A photovoltaic device was obtained. In each substrate unit, four dye-sensitized solar cells were arranged in parallel so that the ratio of the photoelectric conversion element portion in the module substrate area was 50%, and these were connected in series. The area of the dye-sensitized solar cell was the same.
  • Example 2 Except that three organic photoelectric conversion module substrate units were formed on a transparent substrate, and the ratio of the photoelectric conversion element portion in the module substrate area was 35% in each substrate unit, the same as in Example 1. Thus, a photovoltaic device formed by laminating three layers of organic photoelectric conversion module substrates was obtained.
  • Comparative Example 1 A dye-sensitized solar cell in which the catalyst layer of the counter electrode is a platinum thin film, the conductive film of the photoelectrode and the counter electrode is indium tin oxide (ITO), and the configuration other than those is the same as that of Example 1, and the module substrate An organic photoelectric conversion module substrate was formed so that the ratio of the photoelectric conversion element portion in the area was 75%, and a photovoltaic device composed of one layer of the substrate was obtained.
  • ITO indium tin oxide
  • the photovoltaic device obtained in this way was evaluated as follows. [Evaluation of power generation]
  • the photovoltaic device obtained as described above was connected to a source meter (2400 type source meter, manufactured by Keithley), and the amount of power generation in an environment of illuminance: 10,000 lux was measured.
  • the measurement results are shown in Table 2.
  • the value of the power generation amount (and voltage) per device unit area in Comparative Example 1 is used as a reference, and is expressed as a ratio thereto.

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KR102612436B1 (ko) * 2016-10-24 2023-12-08 삼성전자주식회사 광전 소자, 이미지 센서 및 전자 장치

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